Experimental and theoretical study of the mechanism and rate constants of the sequential 5- spirocyclization involving vinyl, aryl and -alkoxyaminyl radicals.

In this research the sequential generation and cyclization of -alkoxyaminyl radicals to produce 1-azaspiro[4.4]nonane, a prominent scaffold in organic and medicinal chemistry, was studied. Competition experiments in benzene at 80 °C with brominated oxime ethers using BuSnH as chain transfer and AIBN as the initiator generated vinyl or aryl radicals which were captured by oxime ethers, allowing approximate 5- cyclization constants at 4.

Structural parameters and physicochemical data from quantum chemical calculations of the peroxyacyl nitrate derivatives RC(O)ONO.

This article present the structural parameters and physicochemical data (Σ , and ) of the methoxyformyl peroxynitrate CHOC(O)ONO (MoPAN), peroxypropionyl nitrate CHCHC(O)ONO (PPN), peroxyacryloyl nitrate CHCHC(O)ONO (APAN), peroxy--butyryl nitrate CH(CH)C(O)ONO (PnBN), peroxycrotonyl nitrate CH(CH=CH)C(O)ONO (CPAN), peroxyisobutyryl nitrate (CH)CHC(O)ONO (PiBN), peroxymethacryloyl nitrate CH=C(CH)C(O)ONO (MPAN) and peroxy--valeryl nitrate CH(CH)C(O)ONO (PnVN) peroxyacyl nitrate derivatives. The equilibrium structures have been performed using the B3LYP and M06-2X functionals combined with the 6-311++G() basis set. The physicochemical data were calculated using several G methods, G3B3, G3MP2B3, G4 and G4MP2.

Carbon monoxide release properties and molecular structures of phenylthiolatomanganese(I) carbonyl complexes of the type [(OC)4Mn(μ-S-aryl)]2.

Several phenylthiolatomanganese carbonyl complexes of the type [(OC)4Mn(μ-SR)]2 (R = Ph (), C6H4-4-CH3 (), C6H4-4-CF3 (), C6H4-4-F (), C6H4-4-Cl (), C6H4-4-OMe (), C6F5 (), and CH2C6H4-4-Cl ()) have been prepared via the reaction of Mn2(CO)10 with diaryldisulfane or via the reaction of [(OC)5MnBr] with arylthiols. These complexes lose two carbon monoxide molecules quite easily yielding tetranuclear [(OC)3Mn(μ3-SR)]4 (). Derivatives with fluoro-substituted aryl groups commonly form mixtures of dinuclear and tetranuclear which can quantitatively be converted to by heating of the corresponding reaction mixtures.